Construction of Renewable Superhydrophobic Surfaces via Thermally Induced Phase Separation and Mechanical Peeling

We report a simple preparation method of a renewable superhydrophobic surface by thermally induced phase separation （TIPS） and mechanical peeling. Porous polyvinylidene fluoride （PVDF） membranes with hierarchical structures were prepared by a TIPS process under different cooling conditions, which were confirmed by scanning electron microscopy and mercury intrusion porosimetry. After peeling off the top layer, rough structures with hundreds of nanometers to several microns were obtained. A digital microscopy determines that the surface roughness of peeled PVDF membranes is much higher than that of the original PVDF membrane, which is important to obtain the superhydrophobicity. Water contact angle and sliding angle measurements demonstrate that the peeled membrane surfaces display super- hydrophobicity with a high contact angle （152°） and a low sliding angle （7.2°）. Moreover, the superhydrophobicity can be easily recovered for many times by a simple mechanical peeling, identical to the original superhydrophobicity. This simple preparation method is low cost, and suitable for large-scale industrialization, which may offer more opportunities for practical applications.

PREPARATION OF MICROPOROUS ULTRA HIGH MOLECULAR WEIGHT POLYETHYLENE (UHMWPE) BY THERMALLY INDUCED PHASE SEPARATION OF A UHMWPE/LIQUID PARAFFIN MIXTURE

Ultra-high molecular weight polyethylene (UHMWPE) with a microporous structure was prepared via thermally induced phase separation (TIPS).Liquid paraffin (LP) was used as a diluent in the preparation of microporous UHMWPE. Small angle laser light scattering (SALLS) and differential scanning calorimetry (DSC) were used to determine the phase separation temperatures,i.e.the cloud points and the dynamic crystallization temperatures,respectively.It was found that the cloudI points were coincident with the cryst...

Effect of Diluent on the Morphology and Performance of IPP Hollow Fiber Microporous Membrane via Thermally Induced Phase Separation

Isotactic polypropylene （iPP） hollow fiber microporous membranes were prepared using thermally induced phase separation （TIPS） method. Di-n-butyl phthalate （DBP）, dioctyl phthalate （DOP）, and the mixed solvent were used as diluents. The effect of α （DOP mass fraction in diluent） on the morphology and performance of the hollow fiber was investigated. With increasing α, the morphology of the resulting hollow fiber changes from typical cellular structure to mixed structure, and then to typical particulate structure. As a result, the permeability of the hollow fiber increases sharply, and the mechanical properties of the hollow fiber decrease obviously. It is suggested that the morphology and performances of iPP hollow fiber microporous membrane can be controlled via adjusting the compatibility between iPP and diluent.

Effects of F127 on Properties of PVB/F127 Blend Hollow Fiber Membrane via Thermally Induced Phase Separation

Hydrophilic poly(vinyl butyral)(PVB) /Pluronic F127(F127) blend hollow fiber membranes were prepared via thermally induced phase separation(TIPS) ,and the effects of blend composition on the performance of hydrophilic PVB/F127 blend hollow fiber membrane were investigated.The addition of F127 to PVB/polyethylene glycol(PEG) system decreases the cloud point temperature,while the cloud point temperature increases slightly with the addition of F127 to 20%(by mass) PVB/F127/PEG200 system when the concentration of F127 is not higher than 5%(by mass) .Light scattering results show that the initial inter-phase periodic distance formed from the phase separation of 20%(by mass) PVB/F127/PEG200 system decreases with the addition of F127,so does the growth rate during cooling process.The blend hollow fiber membrane prepared at air-gap 5mm,of which the water permeability increases and the rejection changes little with the increase of F127 concentration.For the membrane prepared at zero air-gap,both water permeability and rejection of the PVB/F127 blend membrane are greater than those of PVB membrane,while the tensile strength changes little.Elementary analysis shows that most F127 in the polymer solution can firmly exist in the polymer matrix,increasing the hydrophilicity of the blend membrane prepared at air-gap of 5mm.

PREPARATION OF HIGH DENSITY POLYETHYLENE/POLYETHYLENE-BLOCK-POLY(ETHYLENE GLYCOL)COPOLYMER BLEND POROUS MEMBRANES VIA THERMALLY INDUCED PHASE SEPARATION PROCESS AND THEIR PROPERTIES

High density polyethylene （HDPE）/polyethylene-block-poly（ethylene glycol） （PE-b-PEG） blend porous membranes were prepared via thermally induced phase separation （TIPS） process using diphenyl ether （DPE） as diluent. The phase diagrams of HDPE/PE-b-PEG/DPE systems were determined by optical microscopy and differential scanning calorimetry （DSC）. By varying the content of PE-b-PEG, the effects of PE-b-PEG copolymer on morphology and crystalline structure of membranes were studied by scanning electron microscopy （SEM） and wide angle X-ray diffraction （WAXD）. The chemical compositions of whole membranes and surface layers were characterized by elementary analysis, Fourier transform infrared spectroscopy-attenuated total reflection （FTIR-ATR） and X-ray photoelectron spectroscopy （XPS）. Water contact angle, static protein adsorption and water flux experiments were used to evaluate the hydrophilicity, antifouling and water permeation properties of the membranes. It was found that the addition of PE-b-PEG increased the pore size of the obtained blend membranes. In the investigated range of PE-b-PEG content, the PEG blocks could not aggregate into obviously separated domains in membrane matrix. More importantly, PE-b-PEG could not only be retained stably in the membrane matrix during membrane formation, but also enrich at the membrane surface layer. Such stability and surface enrichment of PE-b-PEG endowed the blend membranes with improved hydrophilicity, protein absorption resistance and water permeation properties, which would be substantially beneficial to HDPE membranes for water treatment application.

Fabrication of poly(vinylidene fluoride) membrane via thermally induced phase separation using ionic liquid as green diluent

Ionic liquid(IL),1-butyl-3-methylimidazolium hexafluorophosphate([BMIM]PF6)as a new and environmentally friendly diluent was introduced to prepare poly(vinylidene fluoride)(PVDF)membranes via thermally induced phase separation(TIPS).Phase diagram of PVDF/[BMIM]PF6 was measured.The effects of polymer concentration and quenching temperature on the morphologies,properties,and performances of the PVDF membranes were investigated.When the polymer concentration was 15 wt%,the pure water flux of the fabricated membrane was up to nearly 2000 L·m-2·h-1,along with adequate mechanical strength.With the increasing of PVDF concentration and quenching temperature,mean pore size and water permeability of the membrane decreased.SEM results showed that PVDF membranes manufactured by ionic liquid(BMIm PF6)presented spherulite structure.And the PVDF membranes were represented asβphase by XRD and FTIR characterization.It provides a new way to prepare PVDF membranes with piezoelectric properties.

Synergistic action of non-solvent induced phase separation in preparation of poly(vinyl butyral) hollow fiber membrane via thermally induced phase separation

A systematic study of air gap distance effects on the structure and properties of poly(vinyl butyral)hollow fiber membrane via thermally induced phase separation(TIPS)has been carried out.The results show that the hollow fiber membrane prepared at air gap zero has no skin layer; the pore size near the outer surface is larger than that near the inner surface; and the special pore channel-like structure near the outer surface is formed,which is quite different with the typical sponge-like structure caused by TIPS and the finger-like structure caused by non-solvent induced phase separation(NIPS),because of the synergistic action of non-solvent induced phase separation at air gap zero.The pore size gradually decreases from outer surface layer to the intermediate layer,but increases gradually from intermediate layer to the inner surface layer.With the increase of air gap distance,the pore size near the outer surface gets smaller and a dense skin layer is formed,and the pore size gradually increases from the outer surface layer to the inner surface layer.Water permeability of the hollow fiber membrane decreases with air gap distance,the water permeability decreases sharply from 45.50×10-7 to 4.52×10-7 m3/(m2·s·kPa)as air gap increases from 0 to 10 mm at take-up speed of 0.236 m/s,further decreases from 4.52×10-7 to 1.00×10-8 m3/(m2·s·kPa)as the air gap increases from 10 to 40 mm.Both the breaking strength and the elongation increase with the increase of air gap distance.The breaking strength increases from 2.25 MPa to 4.19 MPa and the elongation increases from 33.9% to 132.6% as air gap increases from 0 mm to 40 mm at take-up speed 0.236 m/s.

Effects of coagulation bath temperature on structure and performance of poly(vinyl butyral) hollow fiber membranes via thermally induced phase separation

Poly （vinyl butyral） （PVB） hollow fiber membranes were fabricated via thermally induced phase separation （TIPS）. The effects of coagulation bath temperature （CBT） on the structure and performance of membranes were investigated in detail. The morphologies of the membranes were studied by scanning electron microscopy （SEM）, the performances of water permeability, rejection, breaking strength and elongation were measured, respectively. The results indicate that all the membranes have the asymmetric morphology and the thickness of the skin layer decreases and the pore size of the outer layer increases with the increase of CBT. The permeability of membranes prepared at air gap 1.0 cm and take-up speed 0.253 m/s increases from 1.047×10-7 to 5.909×10-7 m3/（m2·s-kPa） with the CBT increasing from 20 ℃ to 40℃, and sharply increases to 35.226×10 7 m3/（m2.s.kPa）once the CBT arrives at 50 ℃. While the carbonic ink rejections have no significant decrease, totally exceed 98%, but that of acid-maleic acid copolymer greatly decreases with the increase of CBT. Both the breaking strength and elongation decrease with the increase of CBT.

Effect of Extractant and Cold-drawing on the Structure and Performance of HDPE Hollow Fiber Membranes Fabricated via Thermally Induced Phase Separation Method

Microporous polyolefin hollow fiber membranes were prepared from high density polyethylene （HDPE）-paraffin solution via thermally induced phase separation （TIPS） method. Effects of extraction and cold-drawing condition on membrane structure and performance were investigated.Five volatile solvents were used as extractant. Dimension of hollow fiber and gas permeation rate of membrane were measured. Mierostructure of membrane was examined by Scanning Electronic Microscope （SEM）. The results show that the membrane treated by pentane possesses a higher porosity, nitrogen permeability and lower shrinkage than those of membranes extracted by other three extractants. It is also found that the membrane stretched 133% shows the highest porosity and gas permeability in this study.

Fabrication of Poly(vinylidene fluoride) /Polysulfone Flat Blend Membranes via Thermally Induced Phase Separation Process for Water Treatment

Poly(vinylidene fluoride) /polysulfone(PVDF/PSF) flat blend membrane was prepared via thermally induced phase separation(TIPS) technique.The membrane formation mechanism and membrane structure were investigated and the effects of PSF/PVDF weight ratio on morphology,crystallinity,porosity,and mechanical properties of the membrane were discussed.The relationship between membrane structure and performances,such as pure water flux and the rejection of carbonic black,was also discussed.It was found that solid-liquid(S-L) phase separation occurred for the PVDF/PSF/diluent system.The addition of PSF influences structure and crystallinity of the membrane,which in turn influences mechanical properties and performances of the membrane.The results reveal that it is possible to obtain network structure via S-L phase separation by blending the polymer,which has a partial compatibility with PVDF.

Formation of Polyethersulfone Film with Regular Microporous Structure by Water Vapor Induced Phase Separation

Polyethersulfone(PES)film with regular microporous structure was formed using dichloromethane as the solvent via water vapor induced phase separation(VIPS).The effects of solution concentration,atmospheric humidity and temperature,as well as molecular weight of PES on the surface morphology of the polymer film were investigated.The surface morphology characterized by SEM showed that the pore size reduced as the solution concentration increased.There was an optimum range of relative humidity for the formation of regular pore structure, which was from 60%to 90%at concentration of 20 g·L-1 and 20°C.With the atmospheric temperature varied from 20 to 30°C,the pore became larger and the space between pores increased.The pore size in the PES film with low molecular weight was smaller than that with high molecular weight.

PHASE SEPARATION BEHAVIOR OF ACRYLONITRILE-BUTADIENE-STYRENE COPOLYMER INDUCED BY SURFACES OF VARIOUS POLYMERS

This paper reports the phase separation behavior of ABS films cast on the surfaces of homopelymers or random copolymers.It is found that phase separation of ABS films was induced by the surfaces of the substrate polymers.The relationship between the miscibility of the sub- strate polymers and the phase separation behavior of ABS films was also examined.

Preparation of Porous Silicone Resin Sheet with Phase Inversion in Parallel with Non Solvent Induced Phase Separation and Application to Hollow Particle Formation

We have tried to prepare the porous silicone resin sheet with the phase inversion method in parallel with the non solvent induced phase separation method. In the experiment, ethyl acetate and water were adopted as a good solvent and a poor solvent for silicone resin, respectively and ethyl alcohol as an amphiphilic solvent was used to increase the solubility of ethyl acetate in water and decrease the interfacial tension by mass transfer from water to ethyl acetate. The concentration of silicone resin in ethyl acetate and the oil soluble surfactant species were changed. Increasing the concentration of silicone resin could depress coalescence between the water droplets in the (W/O) dispersion and increase the porosity and pore number density of silicone resin sheet. Span 80 among the oil soluble surfactant species made the porosity and pore number density larger. The effect of physical proparties of liquids concerned on the porosity and pore number density was discussed on the basis of dispersing behavior of liquid droplets in the liquid-liquid dispersion. The hollow silicone resin particles could be prepared by applying the preparation method presented here.

THE ROLES OF REACTION INHOMOGENEITY IN PHASE SEPARATION KINETICS AND MORPHOLOGY OF REACTIVE POLYMER BLENDS

The roles of reaction inhomogeneity in phase separation of polymer mixtures were described and summarized via two examples:photocross-link of polymer mixtures in the bulk state and photopolymerization of monomer in the liquid state. The reaction kinetics,the reaction-induced elastic strain and the phase separation kinetics were monitored respectively by UV-Vis spectroscopy,Mach-Zehnder interferometry and laser-scanning confocal microscopy.It was found that phase separation in the bulk state was strongly inf...

Formation of microporous polymeric membranes via thermally induced phase separation： A review

A review of recent research related to micro- porous polymeric membranes formed via thermally induced phase separation （TIPS） and the morphologies of these membranes is presented. A summary of polymers and suitable diluents that can be used to prepare these microporous membranes via TIPS are summarized. The effects of different kinds of polymer materials, diluent types, cooling conditions, extractants and additive agents on the morphology and performance of TIPS membranes are also discussed. Finally new developments in TIPS technology are summarized.

基于改性逆向热致相分离法聚砜微孔膜的制备与性能

针对逆向热致相分离法(RTIPS)制备聚砜(PSF)微孔膜成膜体系稳定性较差的问题,首先对亲水性的端羟基型超支化聚酯(HBPE)进行封端,然后以PSF为膜材料,通过添加亲水剂封端HBPE构建四元低临界共溶温度(LCST)成膜体系PSF/HBPE/N,N-二甲基乙酰胺/聚乙二醇400,采用改性逆向热致相分离法(m-RTIPS)一步制备了亲水性PSF微孔膜。对封端HBPE进行了结构分析和分子量测试,分析了HBPE的封端率对四元成膜体系浊点和黏度的影响,研究了HBPE的封端率对PSF微孔膜的形貌、渗透性、亲水性、抗污染性和力学性能的影响。结果表明,成功对HBPE进行了封端,封端后HBPE的分子量增加;成膜体系的浊点和黏度随HBPE封端率的升高而增大,但黏度上升的幅度较小;3种添加不同封端率HBPE的PSF微孔膜的纯水通量、截留率、亲水性和力学性能都优于纯PSF微孔膜;随HBPE封端率的增加,膜的纯水通量下降,但截留率差别很小。当HBPE封端率为30%时,PSF膜纯水通量恢复率达88%,抗污染性最佳。添加不同封端率HBPE都可制得表面多孔的膜,当HBPE封端率为50%时,PSF膜具有全双连续结构的形貌,其拉伸强度、拉伸弹性模量和断裂伸长率分别为4.86,143.92 MPa和22.68%,综合力学性能优异。

STRUCTURE AND PERFORMANCE OF POLYAMIDE-6 MEMBRANES PREPARED BY THERMALLY INDUCED PHASE SEPARATION

The asymmetric polyamide-6 （PA6） membranes were prepared by thermally induced phase separation. From the scanning electron microscopy （SEM） images, it is observed that with the increase of silicon dioxide （SiO2） content the structure of obtained membranes gradually varied from cellular structure to large ball-shaped cluster aggregates. Subsequently, with the addition of SiO2, pure water flux increased first and then decreased, while rejection showed the opposite trend. Besides, raising the coagulation bath temperature was favorable to increase pure water flux. Consequently, different membrane morphologies and performance were obtained by changing SiO2 content and coagulation bath temperature.

Fabrication of Dual-pore Scaffolds Using a Combination of Wire-Networked Molding （WNM） and Non-solvent Induced Phase Separation （NIPS） Techniques

In this study, to fabricate dual-pore scaffolds with interconnected pores, Non-solvent Induced Phase Separation （NIPS） and Wire-Network Molding （WNM） techniques were combined. First, a mold with uniform slits was prepared, and needles were inserted into the mold. Subsequently, polycaprolactone （PCL） pellets were dissolved in tetrahydrofuran （THF） at a specified ratio. The slurry was mixed using hot plate stirrer at 1200 rpm for 24 hours at 40 ~C. The PCL slurry was subsequently injected into the mold. Thereafter, to exchange the THF （solvent） with the ethanol （non-solvent）, the mold was soaked in an ethanol bath. After removing the mold from the ethanol bath, the needles were removed from the mold. Consequently, dual-pore scaffold with interconnected pores was obtained. The surface morphology of the fabricated scaffolds were observed using Scanning Electron Microscope （SEM）. Moreover, cell culture experiments were performed using the CCK-8 assay, and the characteristics of cells grown on the dual-pore scaffolds were assessed and were compared with the NIPS-based 3D plotting scaffold.

Poly(vinylidene fluoride-co-hexafluoro propylene) membranes prepared via thermally induced phase separation and application in direct contact membrane distillation

A non-toxic and environmentally safe diluent,acetyl tributyl citrate,was employed to prepare poly(vinylidene fluoride)-co-hexafluoropropylene membranes via thermally induced phase separation.Effects of the polymer concentration on the phase diagram,membrane morphology,hydrophobicity,pore size,porosity and mechanical properties(tensile stress and elongation at break)were investigated.The results showed that the pore size and porosity tended to decrease with increasing polymer concentration,whereas the contact angle,liquid entry pressure and mechanical properties showed the opposite trend.In direct contact membrane distillation operation with 3.5 wt-%sodium chloride solution as the feed solution,the prepared membranes performed high salt rejection(>99.9%).Furthermore,the prepared membranes retained excellent performance in long-term stability tests regarding the permeate flux and salt rejection. ne distillation.